Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 23

1 December 2009

Volume 47, Issue 23

Pages 6333–6734

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      Cyclodextrin polyrotaxanes assembled from a molecular construction kit in aqueous solution (pages 6333–6341)

      Gerhard Wenz

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23610

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      Sophisticated molecular architectures are obtainable in aqueous solution by threading functionalized cyclodextrins onto polymers, with alternating hydrophilic and hydrophobic segments, called poly(bola-amphiphiles). Because the resulting polyrotaxanes are nearly kinetically stable, they can be used without the necessity of further capping reactions. These systems are highly biocompatible and show programmable lifetimes and might be applicable in the biomedical field for instance in cell staining, targeted drug delivery, and gene transfection.

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    1. Synthesis and evaluation of an ester-functional alkoxyamine for nitroxide-mediated polymerization (pages 6342–6352)

      Anna C. Greene and Robert B. Grubbs

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23675

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      An ester-functional alkoxyamine (2) was synthesized by the addition of two equivalents of 1-(4-(methoxycarbonyl)phenyl) ethyl radical across the nitroso group of 2-methyl-2-nitrosopropane and was found to be an effective initiator for the polymerization of styrene, isoprene, and n-butyl acrylate. Basic hydrolysis of the alkoxyamine ester groups and subsequent esterification with 1-pyrenebutanol provided the pyrene-labeled initiator (4) which was used to probe nitroxide retention after polymerization with styrene. High retention of nitroxide (>95%) was confirmed to high conversion of polymer (80%).

    2. Multistimuli responsive grafted poly(ether tert-amine) (gPEA): Synthesis, characterization and controlled morphology in aqueous solution (pages 6353–6361)

      Yanrong Ren, Xuesong Jiang, Rui Liu and Jie Yin

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23676

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      A sample method was used to synthesize multiresponsive grafted poly(ether tert-amine) (gPEA) with different molecular structure. These gPEAs exhibit very sharp response to temperature, pH and ionic strength in the range of 27–77 °C, and can be dispersed in aqueous solution as nano-micelles at room temperature, and then aggregated into mesoglobules at higher temperature. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Supported titanium-magnesium catalysts for ethylene polymerization: A comparative study of catalysts containing isolated and clustered titanium ions in different oxidation states (pages 6362–6372)

      Andrey A. Tregubov, Vladimir A. Zakharov and Tatiana B. Mikenas

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23677

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      A complex [η6-BenzeneTiAl2Cl8] has been supported on MgCl2-surface to obtain a catalyst comprising isolated Ti2+ species. This catalyst is highly active in ethylene polymerization both in the presence and in the absence of organoaluminum cocatalyst. New catalyst comprising isolated Ti3+ species has been obtained after treatment of the surface Ti2+ species with C6F5Cl. The both catalysts are more active in ethylene polymerization in comparison with the conventional catalyst TiCl4/MgCl2, which contain presumably clustered Ti3+ species. It was found supported catalyst comprising titanium ions in different oxidation states produce polyethylene with similar molecular weight and molar mass distribution.

    4. Polynonanolactone synthesized from vegetable oil: Evaluation of physical properties, biodegradation, and drug release behavior (pages 6373–6387)

      Sinoj Abraham and Suresh S. Narine

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23678

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      Synthesis of aliphatic polynonanolactones with different molecular weights was carried out using ring opening polymerization of mono- and di-lactones obtained from vegetable oil. A systematic investigation of the physical properties, biodegradation, and drug release behavior were performed and comparatively evaluated with common petroleum-derived polycaprolactone. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. Biocomplementary interaction behavior in DNA-like and RNA-like polymers (pages 6388–6395)

      Chih-Chia Cheng, Ying-Chieh Yen, Yun-Sheng Ye and Feng-Chih Chang

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23679

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      In the bulk state, highly cross-linked structures through biocomplementary hydrogen bonding and result in substantial increase in Tg relative to their original components. Furthermore, the hydrogen bonding strength of the styrenic polymer (and copolymer) in RNA (U-A) complex is stronger than that in DNA (T-A) base pair. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    6. Facile synthesis of star-shaped copolymers via combination of RAFT and ring opening polymerization (pages 6396–6408)

      Hamilton Kakwere and Sébastien Perrier

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23680

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      Reversible addition fragmentation chain transfer (RAFT) polymerization and bifunctional thiourea organocatalyst mediated ring opening polymerization (ROP) were combined to produce poly(L-lactide) star polymers and poly(L-lactide–co–styrene) miktoarm star copolymers architecture following a facile experimental procedure, and without the need for specialist equipment. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Polyamido amine dendrimers functionalized with poly(phenylenevinylene) dendrons at their periphery (pages 6409–6419)

      Manuela Martín-Zarco, Santiago Toribio, Joaquín C. García-Martínez and Julián Rodríguez-López

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23681

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      We synthesized a series of polyamido amine (PAMAM) dendrimers (Generations 2, 3, 4, and 6) fully functionalized at their periphery with first- and second-generation poly(phenylenevinylene) dendrons. The average number of dendron units attached was determined by MALDI-TOF mass spectrometry, with a lower percentage of functionalization observed on increasing the generation of the PAMAM dendrimer. The materials showed extremely high molar extinction coefficients and emitted blue light with only slightly lower fluorescence quantum yields than the corresponding free dendrons in THF. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Submicron films prepared from aqueous dispersions of nanoscale polymer crystals (pages 6420–6432)

      Qiong Tong and Stefan Mecking

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23682

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      Continuous polyethylene films with a thickess of only 15 nm, up to 220 nm, homogeneous over hundreds of μm, or assembled discontinuous monolayers of flat-on lamella particles were prepared from aqueous dispersions of prefabricated nanoscale crystals by spin-coating at room temperature. Annealing above Tm and subsequent recrystallization afforded again homogeneous continuous films without occurrence of dewetting. For discontinuous monolayers, annealing below Tm resulted in lamella thickening, without changes of crystal orientation or structure of the particle assemblies. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Synthesis and properties of gradient copolymers based on 2-phenyl-2-oxazoline and 2-nonyl-2-oxazoline (pages 6433–6440)

      Hanneke M. L. Lambermont-Thijs, Mark J. H. C. Jochems, Richard Hoogenboom and Ulrich S. Schubert

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23683

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      In this study, the structure–property relationships were investigated for a series of NonOx–PhOx copolymers. The copolymerization kinetics were studied and the reactivity ratios revealed the formation of gradient copolymers. The synthesis of a complete series of NonOx–PhOx copolymers is described whereby the amount of NonOx was increased in steps of 10 mol %. The effect of monomer composition on the thermal and surface properties was investigated in detail. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. Transparent conductive films based on polymer composites containing the mixed-valence tetrathiafulvalene nanofibers (pages 6441–6450)

      Kazuo Tanaka, Fumiyasu Ishiguro, Tomoyuki Kunita and Yoshiki Chujo

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23684

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      We report the facile preparation of the conductive polymer composites containing the mixed-valence tetrathiafulvalene (TTF) nanofibers and their applications as all-organic transparent conductive materials. TTF can be used as a nanofiller for transforming conventional polymers to conductive materials. Self-assemble nanofibers of the neutral and radical cation of TTF can be formed in the polymer solutions during the film deposition, and the resulting composite films with several micron thickness can serve as the conductive material with high transparency. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Hyperbranched framework of interrupted π-conjugated polymers end-capped with high carrier-mobility moieties for stable light-emitting materials with low driving voltage (pages 6451–6462)

      Feng Liu, Ju-Qing Liu, Ran-Ran Liu, Xiao-Ya Hou, Ling-Hai Xie, Hong-Bin Wu, Chao Tang, Wei Wei, Yong Cao and Wei Huang

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23685

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      Combination of ICPs with HCPs to construct novel HICPs (hyperbranched interrupted π-conjugated polymers) based on diarylfluorenes end-capped with high-mobility pyrenes was described to be a novel class of stable light-emitting polymers (LEPs) with low driving voltages. This new design motif could also increase the optical and morphological stability of the materials of blue light-emitting polyfluorene LEP family. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Synthesis of sulfonated poly(diphenylacetylene)s with high CO2 permselectivity (pages 6463–6471)

      Toshikazu Sakaguchi, Koji Kameoka and Tamotsu Hashimoto

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23687

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      Sulfonation of poly(diphenylacetylene)s was achieved by using acetyl sulfate. The sulfonated poly(diphenylacetylene) having t-butyl groups showed high permeability and high permselectivity for CO2. Poly(diphenylacetylene) having trimethylsilyl groups was sulfonated to gave desilylated poly(diphenylacetylene) with sulfonic acid groups, whose degree of sulfonation was as high as 1.55. The sulfonated poly(diphenylacetylene) exhibited the highest CO2 permselectivity among all the substituted acetylene polymers.

    13. Supramacromolecular chemistry: Self-assembly of polystyrene-based multi-armed pseudorotaxane star polymers from multi-topic C60 derivatives (pages 6472–6495)

      Harry W. Gibson, Zhongxin Ge, Jason W. Jones, Kim Harich, Adam Pederson and Harry C. Dorn

      Version of Record online: 22 OCT 2009 | DOI: 10.1002/pola.23688

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      Bingel reactions of malonate esters with C60 produced derivatives bearing 2 to 12 t-BOC protected dibenzylamino moieties; these compounds, some of which consisted of regioisomeric mixtures, were characterized by 1H and 13C NMR and mass spectrometry. Deprotection, protonation, and ion exchange yielded the corresponding dibenzylammonium hexafluorophosphates, which are suitable guest species for dibenzo-24-crown-8; extensive 1H NMR and mass spectrometric results confirm this. Interaction of these polytopic guests with polystyrenes bearing a terminal dibenzo-24-crown-8 moiety resulted in formation of C60-cored star polymers with up to 12 arms, as demonstrated by 1H NMR and viscometric studies.

    14. An environmentally benign room temperature aqueous homo- and copolymerization of styrene and methylmethacrylate catalyzed by [Cp2TiCl2]/NaBPh4 (pages 6496–6503)

      Sudip K. De and Manish Bhattacharjee

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23692

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      An early transition metal metallocene compound, [Cp2TiCl2], has been found to be an effective catalyst for room temperature homo- and copolymerzation of a polar monomer, methyl methacrylate (MMA) and styrene in the presence of NaBPh4 in aqueous medium in the presence of sodium n-dodecyl sulfate. The polymers obtained are of high molecular weight with low molecular weight distribution.

    15. Are o-nitrobenzyl (meth)acrylate monomers polymerizable by controlled-radical polymerization? (pages 6504–6513)

      Jean-Marc Schumers, Charles-André Fustin, Aydin Can, Richard Hoogenboom, Ulrich S. Schubert and Jean-François Gohy

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23693

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      The possibility to control the radical polymerization of the photocleavable o-nitrobenzyl methacrylate (NBMA) and o-nitrobenzyl acrylate (NBA) monomers is discussed. Atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), and nitroxide-mediated polymerization (NMP) have been evaluated. For all methods used, the acrylate-type monomer does not polymerize, or polymerizes very slowly in a noncontrolled manner. The methacrylate-type monomer can be polymerized by RAFT with some degree of control (PDI ∼ 1.5) but leading to molar masses up to 11,000 g/mol only. ATRP proved to be the best method since a controlled-polymerization was achieved when conversions are limited to 30%. In this case, polymers with molar masses up to 17,000 g/mol and polydispersity index as low as 1.13 have been obtained.

    16. Dithieno[3,2-b:2′,3′-d]pyrrole–alkylthiophene–benzo[c][1,2,5]thiadiazole-based highly stable and low band gap polymers for polymer light-emitting diodes (pages 6514–6525)

      Sarada P. Mishra, Akshaya K. Palai, Ritu Srivastava, Modeeparampil N. Kamalasanan and Manoranjan Patri

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23694

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      The synthesis of high-molecular-weight polydithieno[3,2-b:2′,3′-d]pyrroles containing benzo[c][1,2,5]thiadiazole and alkyl thiophenes has been carried out. Polymerizations were carried out by Stille coupling in the presence of CuO to obtain high-molecular-weight polymers. To achieve optimum molecular weight, the amount of CuO required for the polymerizations was investigated. The polymers obtained were found to form excellent film when drop or spin cast from the solution. EL devices were fabricated using the polymers as emissive layer.

    17. Copper catalyzed atom transfer radical copolymerization of glycidyl methacrylate and 2-ethylhexyl acrylate (pages 6526–6533)

      Dhruba J. Haloi, Santanu Roy and Nikhil K. Singha

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23695

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      Atom transfer radical copolymerization of glycidyl methacrylate (GMA) and 2-ethylhexyl acrylate (EHA) was carried out in bulk as well as in solution using methyl 2-bromo propionate (MBrP) as initiator and CuCl/CuBr as catalyst in the combination with N,N,N′,N″,N″-pentamethyl diethylenetriamine (PMDETA) and 2,2′-bypyridine (bpy) as ligands. When PMDETA was used as ligand, the copolymerization leads to the gel formation irrespective to the catalyst used.

    18. The effect of the N-substituent s-trans to the carbonyl group of N-methylacrylamide derivatives on the stereospecificity of radical polymerizations (pages 6534–6539)

      Tomohiro Hirano, Shou Nasu, Akihiro Morikami and Koichi Ute

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23696

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      Radical polymerization of N-methylacrylamide (NMAAm), N,N-dimethylacrylamide (DMAAm), and N-methyl-N-phenylacrylamide (MPhAAm) in toluene at low temperatures gave atactic, isotactic, and syndiotactic polymers, respectively. Monomer conformation suggests that it is the structure of the N-substituent s-trans to the carbonyl group in the monomer that determines the stereospecificity of their radical polymerizations. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Synthesis and characterization of polyfluorenevinylene with cyano group and carbazole unit (pages 6540–6551)

      Suhee Song, Youngeup Jin, Sun Hee Kim, Joo Young Shim, Sooyeon Son, Il Kim, Kwanghee Lee and Hongsuk Suh

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23697

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      The present investigation deals with the synthesis, characterization, and EL properties of new polyfluorenevinylenes, CzCNPFVs, with cyano-substituted vinylene unit and carbazole pendant. In CzCNPFVs, the carbazole pendant was introduced to improve the efficiency of reported CNPFV. The maximum luminescence (Lmax) of CzCNPFV2 of the device with the configuration of ITO/PEDOT/CzCNPFVs/Ca/Al is 1724 cd/m2 at 8 V. The maximum luminescence efficiency of CzCNPFV1 is 0.18 cd/A.

    20. Comparison of surface confined ATRP and SET-LRP syntheses for a series of amino (meth)acrylate polymer brushes on silicon substrates (pages 6552–6560)

      Shijie Ding, J. Alaina Floyd and Keisha B. Walters

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23698

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      For two types of surface confined living radical polymerizations, atom transfer radical (ATRP) and single electron transfer (SET-LRP), reaction conditions and resultant polymer thicknesses are compared for a series of poly(amino (meth)acrylate) brushes polymerized from silane self-assembled monolayers. Characterizations were performed with FTIR spectroscopy, contact angle goniometry, X-ray photoelectron spectroscopy, and spectroscopic ellipsometry. This work demonstrates a novel use of copper metal as the electron donor catalyst in surface confined polymerizations of poly(amine (meth)acrylate) brushes and advantages of SET-LRP versus ATRP for these systems in providing comparable polymer layer thicknesses at lower reaction temperatures and shorter reaction times. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    21. Preparation of crosslinked microspheres and porous solids from hydrocarbon solutions: A new variation of precipitation polymerization chemistry (pages 6561–6570)

      Wei Wu, J. Scott Parent, Saurav S. Sengupta and Bharat I. Chaudhary

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23699

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      A variation of precipitation polymerization chemistry is used to prepare crosslinked microspheres comprised of polymerizable monomer and saturated, aliphatic hydrocarbon. The free radical process involves concurrent C[BOND]H bond addition and oligomerization reactions of a triallyl monomer to generate phase instability within hydrocarbon-rich solutions.

    22. Synthesis and characterization of perfluoro-3-methylene-2,4-dioxabicyclo[3,3,0] octane: Homo- and copolymerization with fluorovinyl monomers (pages 6571–6578)

      Frantisek Mikes, Hongxiang Teng, George Kostov, Bruno Ameduri, Yasuhiro Koike and Yoshiyuki Okamoto

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23700

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      Perfluoro-3-methylene-2,4-dioxabicyclo[3,3,0] octane was synthesized through direct fluorination of the corresponding hydrocarbon precursor by F2/N2. The homopolymer obtained was thermally stable with glass transition temperature (Tg) 180–190 °C. The film made from the homopolymer was transparent with refractive index 1.3290 at 633 nm. The copolymers of the monomer were prepared with chlorotrifluoroethylene, perfluoropropyl vinyl ether, perfluoromethyl vinyl ether and vinylidene fluoride. The copolymers obtained were soluble in hexafluorobenzene and perfluoro-2-butyltetrahydrofuran with Tg 84–145 °C. The films of the copolymers were flexible and transparent with a low refractive index (1.3350–1.3770 at 533 nm).

    23. Kinetic study of H-atom transfer in imidazoline-, imidazolidine-, and pyrrolidine-based alkoxyamines: Consequences for nitroxide-mediated polymerization (pages 6579–6595)

      Mariya V. Edeleva, Igor A. Kirilyuk, Dmitry P. Zubenko, Irina F. Zhurko, Sylvain R. A. Marque, Didier Gigmes, Yohann Guillaneuf and Elena G. Bagryanskaya

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23701

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      The H-atom transfer reaction was studied for a series of imidazoline, imidazolidine, and pyrrolidine-based alkoxyamines by means of 1H NMR. A correlation between the structure of the nitroxyl fragment of alkoxyamine and the intra- and inter-H-transfer reaction was found. The high steric demands of the substituents on the nitroxyl part of the isobutyrate-2-yl alkoxyamine decrease both types of reaction. Controlled polymerization of methylmethacrylate initiated with imidazoline-based alkoxyamine was observed, although the polymer obtained was not living.

    24. Synthesis and hierarchical superstructures of side-chain liquid crystal polyacetylenes containing galactopyranoside end-groups (pages 6596–6611)

      Ming-Shou Ho and Chain-Shu Hsu

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23702

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      The chiral saccharide-containing LC acetylenic monomers exhibited liquid crystalline-like behavior for self-assembly so as to create helical twists morphologies. These helical twist morphological structures can be aligned on the polyimide rubbed glass substrate to form two-dimensional ordered helical patterns. The polymers can also self-assemble into helical nanofibers. These nanofibers are evolved from the helical cables ornamented with entwining nanofibers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    25. Organoboronium amphiphilic block copolymers (pages 6612–6618)

      Chengzhong Cui, Edward M. Bonder and Frieder Jäkle

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23703

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      Amphiphilic organometallic block copolymer with pendant boronium groups were prepared by replacement of one of the bromine substituents on each boryl group of the block copolymer PSBBr2-b-PS with an organometallic reagent ArM (ArM = 2,4,6-trimethylphenyl copper, 4-t-butylphenyltrimethyl tin), followed by treatment with 2,2′-bipyridine. Highly regular micellar aggregates form in MeOH or toluene, which act as selective solvents for the functional boronium and unfunctionalized PS block, respectively. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    26. Use of β-cyclodextrins to control the structure of water-soluble copolymers with hydrophobic parts (pages 6619–6629)

      A. L. Nielsen, M. B. O. Andersen, T. V. Bugge, C. F. Nielsen, T. B. Nielsen, R. Wimmer, D. Yu and K. L. Larsen

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23704

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      Using cyclodextrins to control copolymerization between hydrophobic and hydrophilic monomers.

    27. Synthesis of an oligo(ethylene glycol)-based third-generation thermoresponsive dendronized polymer (pages 6630–6640)

      Wen Li, Dalin Wu, A. Dieter Schlüter and Afang Zhang

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23705

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      The oligo(ethylene glycol)-based third-generation dendronized polymer was synthesized with a much improved strategy, and this polymer shows the characteristic thermoresponsive behaviors with an apparent lower critical solution temperature of 34 °C as its low generation counterparts.

    28. Propagation rate coefficients of isobornyl acrylate, tert-butyl acrylate and 1-ethoxyethyl acrylate: A high frequency PLP-SEC study (pages 6641–6654)

      Bart Dervaux, Thomas Junkers, Maria Schneider-Baumann, Filip E. Du Prez and Christopher Barner-Kowollik

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23706

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      Mark-Houwink-Kuhn-Sakurada (MHKS) parameters as well as Arrhenius relations for the propagation reaction rate coefficient of three synthetically highly relevant acrylate monomers [isobornyl acrylate (iBoA), tert-butyl acrylate (tBuA) and 1-ethoxyethyl acrylate (EEA)] were determined via independent triple-detection size exclusion chromatography (SEC) and Pulsed laser polymerization (PLP) coupled to SEC. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    29. Synthesis of polar block grafted syndiotactic polystyrenes via a combination of iridium-catalyzed activation of aromatic C[BOND]H bonds and atom transfer radical polymerization (pages 6655–6667)

      Lacie V. Brownell, Jihoon Shin and Chulsung Bae

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23707

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      Synthesis of polar graft copolymers of syndiotactic polystyrene was performed using a combination of iridium-catalyzed C[BOND]H activation and atom transfer radical polymerization. 1H NMR, 13C NMR, and FTIR spectroscopies were used to confirm the structures of the graft copolymers. High-temperature size exclusion chromatography confirmed that the functionalization process did not negatively affect the molecular weight compared to that of the starting polymer. Water contact angle measurements demonstrated that the incorporation of the polar graft chains to sPS enhanced the hydrophilicity of the polymers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    30. Facile synthesis of well-defined pH-liable Schiff-base-type photosensitive polymers via visible-light-activated ambient temperature RAFT polymerization (pages 6668–6681)

      Qing Luo, Haimei Zheng, Ye Peng, Huan Gao, Lican Lu and Yuanli Cai

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23708

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      Inspired by the structure character and photosensitive molecular mechanism of natural rhodopsin or bacteriorhodopsin, a novel pH-liable photosensitive polymer whose chromophores directly bind with Schiff base linkages was designed. These polymers were synthesized via a facile, rapid, and well-controlled ambient temperature RAFT polymerization upon irradiating with mild visible light. Schiff base linkages are stable under such mild polymerizing conditions, the chromophore substituents affect the reactivity of monomer, and glycidyl methacrylate may well incorporate in this polymer via random copolymerization. A reversible fluorescence emitting and quenching upon protonating-deprotonating Schiff base linkages of an electron-donating-group-substituted polymer was also observed.

    31. Stepped association of comb-like and stimuli-responsive graft chitosan copolymer synthesized using ATRP and active ester conjugation methods (pages 6682–6692)

      Hongqian Bao, Jinhua Hu, Leong Huat Gan and Lin Li

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23709

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      A well-defined comb-like graft copolymer, poly[(2-dimethylamino)ethyl methacrylate]-graft-chitosan, was successfully synthesized by means of atom transfer radical polymerization and active ester conjugation techniques. The morphology of the graft copolymer in aqueous solution varied gradually with increasing pH value of the media: at pH 4, the Gaussian chains; at pH 5–6, the core-shell structured micelles; at pH 7, the double-layered hard spheres. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    32. Titanium (IV) chloride complexes with salen ligands supported on magnesium carrier: Synthesis and use in ethylene polymerization (pages 6693–6703)

      Marzena Białek and Anna Pietruszka

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23710

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      New supported catalytic systems were developed which contain salen complexes of titanium. They are active ethylene polymerization catalysts, and they also show ability to incorporate higher 1-olefins into the polyethylene chain. Those catalysts may be activated both by methylaluminoxane and by common trialkylaluminium compounds. The comparison of time-related changes in ethylene polymerization rate at 50 °C, for the salen-type complexes of titanium and vanadium, supported on the same magnesium carrier and activated by MAO, shows different type of kinetic profiles: accelerating and decay type for titanium and vanadium catalysts, respectively.

    33. Thiocarbonylthio end group removal from RAFT-synthesized polymers by a radical-induced process (pages 6704–6714)

      Ming Chen, Graeme Moad and Ezio Rizzardo

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23711

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      The radical-induced processes to replace the thiocarbonylthio group make use of the property of thiocarbonylthio compounds to undergo facile reaction with radicals by addition-fragmentation. For fragmentation to occur efficiently in the desired direction, the polymeric radical 5 must be a good homolytic leaving group compared to the attacking radical 1.

    34. Higher α-olefins carbonylation in aqueous media by Pd(II) catalysts modified with substituted diphosphine ligands: Aqueous polyketone latices with high solid contents and molecular weights (pages 6715–6725)

      Mahmoud Sunjuk, Mousa Al-Noaimi, Yahya Al-Degs, Tareq Al-Qirem, Ekkehard Lindner and Adnan S. Abu-Surrah

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23713

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      Water-soluble palladium complexes cis-[Pd(L)(OAc)2] (18) (L represents a dipohosphine ligands of the general formula CH2(CH2PR2)2, where for a: R = (CH2)6OH; b–g: R = (CH2)nP(O)(OEt)2, n = 2–6 and n = 8; h: R = (CH2)3NH2) have been employed, after activation with a large excess of HBF4, for emulsion polymerization of alkenes (propene, butene and their equimolar mixtures) with carbon monoxide. Aliphatic polyketone lattices with a high solid content (21%), high molecular weight (6.3 × 104 g mol−1) and narrow polydispersities (Mw/Mn ≈ 2) were isolated. The catalytic activity of the dicationic palladium (II) based catalysts is highly dependent on the length of the alkyl chain of the ligand. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    35. Macroporous monolithic poly(4-vinylbenzyl chloride) columns for organic synthesis facilitation by in situ polymerization of high internal phase emulsions (pages 6726–6734)

      Sebastijan Kovačič and Peter Krajnc

      Version of Record online: 27 OCT 2009 | DOI: 10.1002/pola.23732

      Thumbnail image of graphical abstract

      Macroporous poly(4-vinylbenzyl chloride) columns were prepared by polymerization of the continuous phase of high internal phase emulsions and functionalised via flow through procedures. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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